Azo dyestuffs



Patented Mar. 24, 1942 UNITED STATES FT NT OFFHCE AZO D'YESTUFFSEberhard Stein, Leverkusen-Schlebusch, Carl Taube, Leverkusen-I.G.-Werk, and Siegfried Petersen, Cologne-Mulheim, Germany, assignors toGeneral Aniline & Film Corporation, New York, N. Y., a corporation ofDelaware No Drawing. Application January 18, 1940, Se-

rial No. 314,452. In Germany January 25,

4 Claims. (Cl. 260-481) The present invention relates to newazodyestufls and to a method of preparing the same; more particularly itrelates to asymmetric azo dyestuffs of the general formula:

I HOOC.OH2.O O.OHZ.COOH

or carboxylic acids thereof or a pyrazolone or also a l-azo compound of2-amino-5-hydroxynaphthalene-'l-sulfonic acid; R and R1 shall, however,be different from each other.

The new asymmetric azodyestuffs can be obtained by coupling 1 molecularproportion of tetrazotized 4.4-diaminodiphenyl3.3-dihydroxyacetic acidwith 1 molecular proportion of 2-amino--hydroxynaphthalene-7-su1fonicacid, its substitution products or l-azo-compounds and 1 molecularproportion of a hydroxynaphthalene or an aminohydroxynaphthalene, thesulfonic or carboxylic acids thereof or a pyrazolone or also al-azo-compound of 2-amino-5-hydroxynaphthalene-T-sulfonic acid, wherebythe two coupling components shall be different from each other. Assubstitution products of 2-amino-5- hydroxynaphthalene-7-sulfonic acidmay be used N-alkyl, N-aralkyl-, N-aryl-, N-acyl-, N-aroylderivatives,halogen or Soul-substitution products and as 1-azo-compounds the monoanddis azodyestuffs obtainable by coupling 2-amino-5-hydroxynaphthalene-l-sulfonic acid in acid medium with a diazo compound,coupling taking place in this case in the l-position. As second couplingcomponents may be used 1- and 2-hydroxynaphthalene, the amino,alkylamino, arylamino, acylarnino, aroylamino, -SO3H and COOHderivatives thereof, pyrazolones and 1-' azo-compounds ofZ-amino-5-hydroxynaphthalene-7-sulfonic acid.

The new dyestuffs dye cellulosic fibers in general grey to black shades.When aftertreating the dyeings with agents yielding metals, especial- 1ywith copper salts, the fastness properties of the dyeings becomeimproved. The new dyestuffs are distinguished over the dyestuffs knownfrom German specification 61,053 by better fastness properties,especially by better fastness to light and washing. In comparison withthe dyestuffs known from French specification 813,154 the new dyestuffshave the advantage that by them the series of the fast dyestuffsmetallizable on the fiber has been extended to subdued grey, blackishblue and black shades.

The following examples illustrate the invention without, however,limiting it thereto.

Example 1 To the aqueous tetrazo solution of 0.029 mol4.4-diamino-3.3-diphenoxy-acetic acid (corresponding to 4 g. of sodiumnitrite) which has been neutralized with sodium bicarbonate or sodiumacetate the solution of 0.029 mol of the sodium salt of thedisazodyestuff of the formula:

HOaS- NHz C O OH (corresponding to 2 g. of sodium nitrite) and 6 g. ofanhydrous sodium carbonate in 500 cc. of water are slowly added withstirring and continuous cooling to 0 C. The mixture is stirred at thistemperature until free tetrazo compound can no longer be detected. Nowthe reaction product is run into a solution consisting of 0.034 mol of2-amino-B-hydroxynaphthalene-6-sulfonic acid (corresponding to 2.1 g. ofsodium nitrite) and 15 g. of anhydrous sodium carbonate in 250 cc. ofwater, keeping the solution at 0 C. and stirring until the coupling iscomplete. The dyestuff is filtered off and in order to purify itseparated again from Weakly sodium carbonate alkaline "solution byadding sodium chloride.

mula:

The dyestuff If in the above combination the 2-amino-8-hydroxynaphthalene-G-sulfonic acid is replaced by equivalent quantitiesof the coupling components enumerated in the following table dye- JOOHand dyes cotton dark grey shades; the dyeing aftertreated with coppersalts is also dark grey.

HOzS

HOOQCHa CHLCOOH ing shades:

stuffs are obtained yielding on cotton the follow- Dyeing on Couplingcomponen igfil g c d v i t li copper salts R=radical of theZ-amino-S-hydroxynaphthalene-B-sulionic acid.

O OH RNH- Bluish grey. Grey.

R-NHC 00H do Do.

R-N H do Do.

RNH.CO.CH3 do A. Do.

e R-NH. S Oz-QOH ..do l. Bluish grey.

C O OH 0 Ha CH3 R SO: 0H do. Do.

0 O OH E RNHCH 0H .d0 Grey.

0 O OH R-NH-QOCH do Do.

HO3S'" C 0 0H Reddish grey. Reddisli grey.

R'=radical of the 2-amino-5-hydroxynaphthalene-7-sulfonic acid.

NH.C O-ONH2 Bluish grey--. Bluish grey.

l NH.CHIC -OH "do Do.

0 O OH "=2-nmino-5-hydroxynaphthalene-7-sulfonic acid, -N=N is attachedto the 1- position.

R-N=NC 0H Grey Grey.

0 O O H Dyeing on Coupewmpm ate alerts; copper salts R '-N=NC O GreyGrey.

n 01:1 do Do.

COOH

"N=N CO.NHQOH do D0.

N--C-OOOH R-N=NC Bluish grey-" Bluish grey.

NH-N

Example 2 equivalent quantities of the coupling components To theaqueous tetrazo solution of 0.029 mol 4.4-diamino-3.3-diphenoXy-aceticacid (correenumerated in the following table dyestuffs are obtainedyielding on cotton the following shades:

sponding to 4 g. of sodium nitrite) which has been neutralized withsodium carbonate or so- Dyeing 011 cotton 0 1 t a dium acetate theso1ut1on of 0.029 mol of the Oupmg componens Dyem on cottonfifiiffiiiillfl sodium salt of the monoazodyestuff of the for- 1111113R=radica1 of the 2-amino-8 hydroxyiaphthalene 6 sul- I N OH coon H038NHz 00E R-NH Dull navy blue Dull navy blue.

R-NHOOOHa. do Do. OH l c0011 (corresponding to 2 g. of sodium nitrite)and 6 g. of anhydrous sodium carbonate in 350 cc. of water OH B1 h m areslowly added with stirring and cooling to ms Bhush 0 C. stirring iscontinued until free tetrazo com- 1 4 pound can no longer be detected.Thereupon 5 R NH'cocfis the reaction product is run into a solutionconsisting of 0.034 mol of Z-amino-B-hydroxynaphthalene-G-sulfonic acid(corresponding to 2.1 g. -C Grey Greyof sodium nitrite) and 15 g. ofanhydrous sodium I carbonate in 250 cc. of water, keeping the solutionOH 0 0 0H always at 0 C. and stirring until coupling is complete.

The preparation of the dyestufi can take place also in the reverse orderas shown in Example 1. H035 Bluish "m B} h The final coupling can becarried out in this case \30011 without addition of pyridine.

1 h The dyestuff after isolation and purification 1n h $%;?n hh $f theusual manner dyes cotton bluish grey shades; fomc acidthe dyeingsaftertreated with copper salts are R-NH.o0NH2 d0 Do. also bluish grey.In its free state the dyestufi I corresponds to the following formula:

HO- N=1TT s0 H HO s 11000 HzN- 3 a N=N- QN=N NH:

I OH o o OH nooaom CH2.COOH

Example 3 If in the above combination the2-amino-8-hydroxynaphthalene-fi-sulfonic acid is replaced by To theaqueous tetrazo solution of 0.029 mol 4.4-diamino-3.3'-diphenoxy-aceticacid (corre- Example 4 sponding to 4 g. of sodium nitrite) which hasbeen neutralized with sodium bicarbonate or To the aq s e r o S n of -0m01 sodium acetate the solution of 0.029 mol of the ia ph y a d resodiumsalt of the disazodyestufi of the formula: 5 SD g to 4 of d um ni te) Wch as been neutralized with sodium bicarbonate or so- Y T dium acetatethe solution of 0.029 mol of 4-ami- ANOON Q nobenzoyl 2amino-5-hydroxynaphthalene-7- HOaS N112 coon sulfonic acid(corresponding to 2 g. of sodium nitrite) and 9 g. of anhydrous sodiumcarbonate I in 350 cc. of water are slowly added with stirring 0H andc00ling to 0 C. Stirring at 0 C. is coni tinued until the tetrazocompound is completely (corresponding to 2 g. of soduun mtrite) and 6gused up. Thereupon the reaction product is run o a ydrous sodiumcarbonate in 500 cc. o into a solution consisting of 0.034 mol of2.8-diwa a w y d d w stirring a d cooling hydroxynaphthalene-6-sulfonicacid-3-carboxylio to 0-; s i r ng is c t nu d until free tetrazo acid(corresponding to 2.1 of sodium nitrite) compound can no longer bedetected. Thereupon d 15 g. of anhydrous sodium carbonate in 300 thereaction product is run into a solution concc. of water, keeping thesolution always at 0 C. sisting of 0.034 mol of 2-amino-8-hydroxynaphandstirring until the coupling is complete. thalene-G-sulfonic acid(corresponding to 2.1 g. The dyestuff is isolated in the usual manner.of sodium nitrite) and 15 g. of anhydrous sodium It corresponds in itsfree state to the following carbonate in 250 cc. of water, keeping thesoluformula:

rnN-O CO.NH- 3H HO3S\ /COOH 0H t t ta HOOC.CHz onicoon tion always at 0C. and stirring until the couand dyes cotton bluish grey shades, thedyeings pling is complete. aftertreated with copper salts are alsobluish The preparation of the dyestuff may take place grey.

also in the reverse coupling order as explained in Example 1.

The isolated and purified dyestufi dyes cotton '10 dark grey shades.When aftertreated with copper salts also dark grey shades are obtained.The

dyestufi corresponds in its free state to the following formula:

SOaH 110 s coon HgN- x I on on nooocm cnicooir If in the abovecombination the 2-amino-8-hydroxynaphthalene-fi-sulfonic acid isreplaced by Example 5 equivalent quantities of the coupling componentsenumerated in the following table dyestuffs are obtained yielding oncotton the following shades:

0 408 g. of the potassium salt of 4.4-diamino- 3.3-diphenoxy-acetic acidare dissolved in ice cold water and after adding 600 g. of hydrochloricacid (sp. gr. 1.18) diazotized with 138 g. of sodi- Dyeing on C uflincommems Dyeing on cotton aft-GP um nitrite. After some time the solutionis ren- 0 I b I cotton t regge d dered acetic by adding sodium acetate.Thereupon the aqueous solution of 367 g. of the sodium salt of2-(4'-anisidy1) 5-hydroXynaphthalene-7- R NHOCOOH Grey Gm sulfonic acidis slowly added. The coupling is complete after 4 hours and theintermediate is sucked off and anew pasted with water The x h R ddh 1ggiieiyl 5 pynzolonc 3 carbox; 11c Reddls grey o is grey paste thusobtalned 15 added t a St g y So um carbonate alkaline solution of 353 gof 2-benzoyl- R: d l of the 2-ammo-S- amino 5hydroxynaphthalene-7-sulfonic acid; 801d. the couphng takes some timeand is carried out towards the end at room temperature. The dyestuff isfiltered off pressed and dried. The dyewherein R stands for the radicalof a l-aryl azo stufi corresponds in its free state to thefollowcompound selected from the group consisting of ing formula:monoand disazo compounds of 2-amino-5-hy- SOaH HOsS O I Q NH.CO.G0H5

H I 6H 3000.011: CH2GOOH and dyes cotton and regenerated cellulose darkdroxynaphtha1enesulf nio acid, aryl being a navy blue shades. By anaftertreatment with radicle of the benzene series and R1 stands forcopper salts the dyeings become fast to light and t e radical o aCoupling p ent Selected wa hin from the group consisting of 1- andZ-hydroxy- A somewhat more reddish navy blue is obtained ap e amino: y-u aryl-amiby combining tetrazotized 4.4'-diamino-3.3-dino-, acylamino,aroylamino-, SOsH and phenoxyacetic acid on the one side with 1- COOHderivatives thereof, pyrazolones and 1- chloro 2amino-5hydroxynaphthalene-7sularyl azo compounds selec ed fr m e ro pfonic acid and on the other side with 2-benzoyl- Consisting of monoand dsa o c p unds of amino5-hydroxynaphthalene-7sulfonic acid or m noy y pfl acid, the derivatives thereof substituted in the aroyl aryl being aradicle of the benzene series, the radical. 2s radicals R and R1 beingdifierent from each Example 6 other, dyeing cellulosic fibers in generalgrey to black shades the fastness properties of which become improved byan aftertreatment with agents yielding metals.

2. As new products asymmetric azodyestufis of the general formula:

408 g. of the potassium salt of 4.4-diamino- 3.3-diphenoXy-acetic acidare diazotized as stated in Example 5 and to the solution sodium acetateis added until the acid reaction to Congo red paper has disappeared. Atlow temperature an aqueous solution of 364 g. of the potassium salt ofZl-benzoylamino-5-hydroxynaphthalene-7- RN=NC N=NR1 sulfonic acid and500 g. of sodium bicarbonate as I is slowly added drop by drop. Theviolet-blue 0 4) coupling product is sucked off after some hours(BHFOOOH and the paste is added to an ice cold sodium carbonate alkalinesolution of 375 g. of 2-(2.4'- wherein R stands for the radical of al-aryl azo dimethoxyphenylamino)5-hydroxynaphthalenemp nd selected fr hgroup is n of 7-sulf0nic acid. If necessary the coupling is finmonoanddisazo compounds of 2-amino-5-hyished with the addition of pyridine andworked droxynaphthalene-7-sulfonic acid containing an up as usual. Thedyestufi which corresponds in o-hydroxycarboxylic acid grouping arylbeing a its free state to the following formula: radicle of the benzeneseries and R1 stands for S 0 @H H OaS core III-000m N=N CH l i i HOOCCH2 CH2.COOH

and dyes 11 1 i fibers navy b1u had By the radical of a couplingcomponent selected from an aftertreatment with copper salts the fastnessthe group Consisting of and Yd y D properties of the dyeings becomeimproved. n t a n a y am a la inw,

The 2 (2.4 dimethoxyphenylamino) -5-hyacylamino-, aroylamino-, SO3H andCOOH droxynaphthalene7-sulfonic acid used above is iv v of a -hy roxy pa me pyobtainable for instance by allowing 1.6-dihydroxrazolones andl-aryl azo compounds selected ynaphthalene-3-sulfonic acid to react with1- o th group Consisting of monoand disazo amino-2.4-dimethoxybenzene inaqueous solution compounds of 2-amino-5hydroxynaphthalenein the presenceof sodium bisulfite or by boiling -sulfonic acid, aryl being a radicleof the ben- 2amino5-hydroxynaphtha1ene-7 sulfonic acid zene series, theradicals R and R1 bein different and 1 1 2 4 t i aqueous from eachother, dyeing cellulosic fibers in gen- Solution t Sodium mt andammonium bieral grey to black shades the fastness properties sulfite. ofwhich become improved by an aftertreatment We claim: with agentsyielding metals.

1. As new products asymmetric azodyestufis of 3. As new p o s sy t c adyes ffs the general formula of the general formula:

I H00CCH2 GHQ-C0011 wherein R stands for the radical of a l-aryl azocompound selected from the group consisting of monoand disazo compoundsof 2-amino-5-hydroxynaphthalenefl-su1fonic acid, containing ano-hydroxycarboxylic acid grouping aryl being a l HOOC HQN erties ofwhich become improved by an aftertreatment with agents yielding metals.

4. As new product the asymmetric azodyestufi corresponding in its freestate to the formula:

H O O OH and dyeing celiulosic fibers bluish grey shades.

EBERI-IARD STEIN.

CARL TAUBE. SIEGFRIED PETERSEN.

